Problem Set 1 Solutions

Problem 1: van der Waals and Mechanical Stability

p
RT
=

1 b

a
RT

2
To nd the lowest temperature where the vdw equation satises mechanical stability we
need set (v/p)
T
0 and solve for T. However, the above equation of state is given as p
as a function of v = 1/. So we need to use a few properties of derivatives to make our life
easier:
(v/p)
T
=
1
(p/v)
T
0
(p/v)
T
0
(p/v)
T
=

v
_
RT
v b

a
v
2
_
T
=
RT
(v b)
2
+
2a
v
3
0
T
2a(v b)
2
Rv
3

3
2a(1/ b)
2
R
1
Problem 2: van der Waals parameters
b is a measure of the excluded volume of an atom or molecule. Thus, we can just set b equal
to the volume of an N
2
molecule, assume N
2
is spherical and solve for the diameter:
b = 4/3r
3
r =
_
3b
4
_
(1/3)
=
_
3(40 cm
3
/mol 1/6.022 10
23
mol
1
)
4
_
(1/3)
= 2.51

A
D = 5.02

A
Problem 3: Second Virial Coecient for Particles with Square Well Poten-
tial
B
2
= 2
_

0
r
2
dr
_
e
u(r)/k
B
T
1
_
u(r) =
_
_
_
, r
, < r <
0, r
2
a)
!
"#$%!
&!!
"! #"!
$!
b)
B
2
= 2
_

0
r
2
dr
_
e
u(r)/k
B
T
1
_
= 2
_

0
[0 1] r
2
dr 2
_

_
e
/k
B
T
1
_
r
2
dr 2
_

[1 1] r
2
dr
=
2
3
3

2
3
3
(
3
1)(e
/k
B
T
1)
=
2
3
3
_
1 (
3
1)(e
/k
B
T
1)
_
c) The asymptotic limit of B
2
can be calculated by letting T :
B
2
=
2
3
3
_
1 (
3
1)(e
/k
B

1)
_
=
2
3
3
_
1 (
3
1)(1 1)

=
2
3
3
The zero of B
2
is the Boyle temperature and will be calculated in part d. The graph ofB
2
3
is:
!
"#$%&!'&()&*+,-*&!.,#!
/&!0+%0-%+,&1!23!)+*,!14!
'!
"5!
5!"
6
76!
89$(),#,20+%%$!+))*#+0:&9!
3&;+,2<&!23=232,$!+9!'!;#&9!,#!>!
d) The Boyle temperature is given by the temperature at which B
2
= 0:
B
2
=
2
3
3
_
1 (
3
1)(e
/k
B
T
1)
_
= 0
0 = 1 (
3
1)(e
/k
B
T
1)
e
/k
B
T
=
1

3
1
+ 1
=

3

3
1
T =

k
b
ln
_

3
1

3
_
c) Recall from lecture that the second virial coecient for the van der Waals gas is
B
2
= b
a
T
. In the limit of high T the exponent in B
2
from the square potential can
be expanded:
4
B
2
=
2
3
3
_
1 (
3
1)(e
/k
B
T
1)
_
=
2
3
3
_
1 (
3
1)(1 + /k
b
T 1)

=
2
3
3

2
3
3
(
3
1)

k
B
1
T
matching terms between the two virial coecients gives:
b =
2
3
3
a =
2
3
3
(
3
1)

k
B
Problem 4: The Lennard-Jones Potential and the Law of Corresponding States
U(r) = 4
_

12
r
12


6
r
6
_
where has units of energy and has units of length.
a) The rst term in the Lennard-Jones potential, the 1/r
12
term, accounts for short range
repulsions. These short range repulsions are due to the electron-electron repulsion of the
atoms, which can also be attributed to pauli-exclusion. The second term in the Lennard-
Jones potential, the 1/r
6
term, accounts for long range interactions. These long range
interactions originate from london, induced-dipole induced-dipole, forces.
b) To write the Lennard-Jones potential in reduced units we only need to change U(r) to
U

(r)

= U(r

)/ and r to r

= r/. This gives:

U

(r

) = 4
_
1
(r

)
12

1
(r

)
6
_
5
c)
= f
1
(, , m)

,
k
B
T = f
2
(, , m) T

,
p = f
3
(, , m) p

, and
t = f
4
(, , m) t

,
The dierent f
i
functions correspond to dierent arrangements of the parameters, , ,
and m such that each f
i
has the same units as the corresponding unreduced quantities, ,
k
B
T, p and t.
Thus, f
1
needs to have units of 1/volume. (note that these are number densities). The
only way to obtain units of volume using the parameters is f
1
= 1/
3
.
f
2
needs to have units of energy. Thus, f
2
= .
f
3
needs to have units of pressure, which are force/area or energy/volume. Thus, f
3
= /
3
.
f
4
needs to have units of time, which is a bit more complicated to achieve using energy,
volume and mass. The logic I used to obtain f
4
was as follows:
First, the only place there is time in the given parameters is in the unit of energy. In SI
units energy is a Joules, which is equal to kg m
2
/s
2
. Here, time is on the bottom and is
squared so we know f
4
is going to have to be proportional to 1/

to get time on the

top and not squared. Thus, we now have f
4

s
m
1

kg
. To cancel the meters and square
root of kilograms on the bottom we just need to add a and

m on the top yielding
f
4
=
_
m/ .
d) The Law of Corresponding states that all gases have the same properties at the same
value of reduced quantities. Though we havent gotten to critical points yet in class, what
this law is saying is that absolute values of temperature, pressure etc. dont matter. In-
stead, only the relative distance from the critical points matter. Reduced coordinates are
a measure of how far a gas is from its critical point. Consequently, all gases at the same
reduced units are equally distant from their corresponding critical points and hence have
the same properties.
e) We can use the formulas from part c to nd the reduced units that the argon conditions
correspond to. Then using the same formulas we can nd the corresponding conditions for
xenon and helium. (note that densities need to be converted to number densities)
6
calculation of reduced units:

=
3

= (0.341 10
9
m)
3
)(840kg/m
3
)
_
mol
39.948 10
3
kg
__
6.022 10
23
molec
mol
_
= 0.5
T

=
k
B
T

=
(1.38 10
23
J/K)(60 K)
1.656 10
21
J
= 0.5
calculation of the corresponding state for xenon:
=
0.5
(0.406 10
9
m)
3
_
131.293 10
3
kg
mol
__
mol
6.022 10
23
molec
_
= 1629 kg/m
3
T =
(3.092 10
21
J)(0.5)
1.38 10
23
J/k
= 112 K
calculation of the corresponding state for helium:
=
0.5
(0.256 10
9
m)
3
_
4.003 10
3
kg
mol
__
mol
6.022 10
23
molec
_
= 198 kg/m
3
T =
(1.410 10
22
J)(0.5)
1.38 10
23
J/k
= 5 K
7
Problem 5: Statistics of Coin Flips
N =
M

i=1
n
i
where N is the total number of heads, M is the total number of ips (or number of people
each ipping one coin), and n
i
equals 0 when coin i is a head and 0 otherwise. For this
problem were assuming that the average value of N is:
N = M/2
a)
(N)
2
= [N N]
2

= N
2
N
2
N
2
= M
2
/4
N
2
=
_
M

i
n
i
M

j
n
j
_
=
M

i,j
n
i
n
j

=
M

i=j
n
i
n
i
+
M

i=j
n
i
n
j

To continue we need to notice a few things. First since n

i
equals either 0 or 1 then n
2
i
= n
i
.
Second, since each ip (or person) is not inuenced by any other ip n
i
and n
j
for i = j
are uncorrelated. This implies that n
i
n
j
= n
i
n
j
. Also, the average of any n
i
is the
same as the average for any other n
i
. Therefore, n
i
= n
j
= n
1
= 1/2. We can use
these results to nish o the calculation of N
2
:
8
N
2
=
M

i=j
n
i
+
M

i=j
n
i
n
j

= n
i

i=j
1 +n
i
n
j

i=j
1
= n
1
M +n
1

2
M(M 1)
= M/2 + M
2
/4 M/4
= M/4 + M
2
/4
(N)
2
= M/4 + M
2
/4 M
2
/4
= M/4
b)
_
(N)
2
/N =
_
M/4
M/2
= 1/

M
c)
i) M = 1
_
(N)
2
/N = 1/

1 = 1
ii) M = 100
_
(N)
2
/N = 1/

100 = 0.1
iii) M = 10, 000
_
(N)
2
/N = 1/

10, 000 = 0.01

iv) M = 10
8

_
(N)
2
/N = 1/

10
8
= 0.0001
9